Fabrication of Wear and Corrosion Resisting G3 Alloy-like P110 (2015)

8/17/2019 Fabrication of Wear and Corrosion Resisting G3 Alloy-like P110 (2015)

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Int. J. Electrochem. Sci., 10 (2015) 6057 - 6069

International Journal of

ELECTROCHEMICAL

SCIENCE www.electrochemsci.org

Fabrication of Wear and Corrosion Resisting G3 Alloy-like

Coating on P110 Steel by Double Glow Plasma Alloying

Wei Tian1 ,2 , Wenhai Yu2 , Naiming Lin1,* Jiaojuan Zou1 , Junwen Guo1 , Hongyan Zhang 1 , Peng Zhou1 ,

Ruizhen Xie1 , Yong Ma1 , Zhenxia Wang 1 , Xiaofei Yao3 , Pengju Han4 , Xiaoping Liu1 , Bin Tang 1

1 Research Institute of Surface Engineering, Taiyuan University of Technology, Taiyuan, 030024, P. R.

China2 China United Northwest Institute for Engineering & Research, Xiàn, 710082, P. R. China3 School of Materials and Chemical Engineering, Xiàn Technological University, Xiàn, 710032, P R

China4 Department of Civil Engineering, Taiyuan University of Technology, Taiyuan, 030024, P. R. China*E-mail: [email protected]

Received: 10 April 2015 / Accepted: 15 May 2015 / Published: 24 June 2015

There is a need for oil casing tubes to resist both wear and corrosion attacks during operation. In the present work, a G3 alloy-like coating has been formed on P110 oil casing tube steel via double glow

plasma surface alloying using a G3 alloy source electrode to improve its surface performance and

prolong its service life-time. X-ray diffraction (XRD), scanning electron microscope (SEM), optical

microscope (OM), glow discharge optical emission spectroscope (GDOES) and micro hardness tester

were employed to analysis the phase constitution, surface morphology/composition, cross-sectional

microstructure, element distribution and surface hardness value of the G3 alloy-like coating. The wear

resistance of the G3 alloy-like coating was measured by reciprocating type tribometer under dry

sliding against GCr15 steel and Si3 N4 counterparts. Electrochemical measurements, open circuit

potential and potentiodynamic polarization were conducted in some CO2-saturated simulated oilfield

brine to evaluate the anti-corrosion property of the G3 alloy-like coating. The results revealed that the

received G3 alloy-like coating was uniform and compact. The G3 alloy-like coating with highersurface hardness had significantly improved the anti-wear property of P110 steel. The G3 alloy-like

coating had better corrosion resistance revealing by higher open circuit potential and lower corrosion

current density as compared with P110 steel. The formation of G3 alloy-like coating has made it

possible to enhance the anti-wear property and corrosion resistance of P110 steel.

Keywords: wear; corrosion; G3 alloy; coating; oil casing tube; P110 steel; double glow plasma

surface alloying

http://www.electrochemsci.org/mailto:[email protected]:[email protected]:[email protected]:[email protected]://www.electrochemsci.org/


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Int. J. Electrochem. Sci., Vol. 10, 2015 6058

1. INTRODUCTION

Human culture has recognized the importance of materials degradation and protection ever

since the very beginning of civilization [1]. In nowadays, material engineers are constantly confronted

with the challenge to design and produce new materials that are both wear and corrosion resistant over

wide range of modern industrial environments and applications [2]. One way of achieving this is via

surface modification technique involving coating formulations through compositional modifications as

well as improved surface processing techniques [2]. It is well accepted that surface modification takes

the advantage of offering a compromise between the performance against degradations and the cost

with promising properties to prevent or minimize the wastage of materials [3].

The rapid economic growth and industrial development around the world have contributed to

huge consumption of oil/gas over the past decades, and much more oil/gas wells are required to exploit

[4]. Petroleum tube is a key structural unit of an oil well. It takes about 1/3 of the whole cost ofdeveloping an oil well, and the oil casing tube holds almost 3/4 of the entire petroleum tube consumes

[4, 5]. The oil casing tubes are prone to degradation and failure that caused by wear and corrosion

when they are operated in oil/gas wells [4]. It was reported that oil casing tube directly influence the

life-time of an oil well, the oil well might determine the oil field service time [4]. According to the

investigations and understandings about corrosion of oil casing tubes, corrosion protection methods,

such as application of anticorrosion alloy, injection of inhibitor, cathode protection and surface

treatment have been used [6]. Actually using anticorrosion alloy tubes is the most effective way to

guarantee high efficient and safe production, e.g. Ni-base alloys: Inconel 625, Inconel 718, G3 and

Incoloy 825 [7]. However, the mentioned above anticorrosion alloy contains large amounts of noblemetals (e g, Ni, Cr, Mo), and this would bring out the increasing in petroleum production cost [5]. In

many engineering applications, surface performance has significant impacts on the life of metallic

work pieces [8]. Most types of material degradation, such as wear, corrosion/oxidation and

fatigue/fracture are often generated on the surfaces of engineering components. However surface

modification techniques can overcome the aforementioned problems [9].

In the present work, attempts were therefore conducted to simultaneously impart P110 steel

high wear and corrosion resistance by fabricating a G3 alloy-like coating via double glow plasma

surface alloying (DGPSA) [10]. The microstructural characterizations and surface hardness of the

obtained G3 alloy-like coating were systemically investigated. The anti-wear property and corrosion

resistance of the G3 alloy-like coating and P110 steel were comparatively estimated.

2. EXPERIMENTAL PROCEDURE

2.1 Processing

P110 steel substrate materials were prepared from a P110 steel tube in the size of 25 × 12 × 5

mm3. G3 alloy source electrode was prepared from a G3 alloy tube. Chemical compositions of P110

steel and G3 alloy are suggested in Table 1 [11, 12]. Before plasma surface alloying treatment, all the

P110 steel specimens were mechanically ground using emery papers and degreased in acetone. The


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DGPSA treament was conducted on independent equipment. Figure 1 suggests the schematic diagram

of DGPSA apparatus. The technological principle of DGPSA had been described in other published

papers [10, 13 – 18]. In the present work, argon (Ar) gas was chosen as the carrier gas. Firstly, the P110

steel specimens were subjected to ion bombardment in an Ar glow discharge for 30 min. The DGPSA

process was performed at target (source electrode) voltages ranging in -750~-650 V under atemperature range of 950~1000 ℃, P110 steel substrate (work piece) was conducted at voltages

between -700~-500 V to heat the P110 steel substrate up to a temperature of 900 ℃, the distance

between the source electrode and the work piece was 15 mm. The gas pressure in the chamber was

kept about 35~40 Pa through the DGPSA process. The whole DGPSA duration was of 4 h. Then the

DGPSA treated P110 steel sample was cooled under the argon flow in the vacuum chamber [13].

Figure 1. Schematic diagram of DGPSA apparatus

Table 1. Chemical compositions of P110 steel and G3 alloy (Wt. %)

Element C Si Mn P S Cr Ni Mo Cu Nb V Ti Fe

P110

steel0.26 0.19 1.37 0.009 0.004 0.148 0.028 0.013 0.019 0.06 0.006 0.011 balance

G3

alloy0.009 0.12 0.51 0.007 0.001 22.05 balance 6.79 1.76 0.10 / / 20.02

2.2 Characterizations and testing

Microstructural analyses and thickness measurements of a G3 alloy-like coating were carried

out under the OM. Nital-etched micro-section perpendicular to the surface of the sample was

examined. The elemental composition profile along the thickness to the G3 alloy-like coating was

examined using GDOES. The surface morphology of the obtained coating was investigated by employ

of SEM. The phase constitution of the G3 coating was evaluated using XRD. A micro-hardness tester

was used to measure the surface hardness of G3 alloy-like coating and P110 steel via a Vickers

indenter.

MFT-R4000 reciprocatory type friction-wear testing machine was used to estimate the wearresistance of P110 steel and G3 alloy-like coating. The atmospheric condition in the laboratory has


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involved a temperature of 298 K and a relative humidity of 40~45 %. GCr15 steel and Si3 N4 balls with

the size of Φ 5 mm were selected as the counterparts. All the tests were performed under the following

conditions: by wearing against counter balls with a reciprocatory displacement of 5 mm, a load of 10 N,

a sliding velocity of 2 Hz for 30 min. An analytical balance with an accuracy of 0.01 mg was used to

get the mass losses of the tested samples. The worn surfaces of the tested samples were also observedusing SEM [19].

The corrosion resistance of the G3 alloy-like coating was examined by electrochemical

measurements, open circuit potential (OCP) and potentiodynamic polarization [11, 20, 21]. The

corrosion medium, CO2-saturated simulated oilfield brine was prepared from reagent grade chemical

and distilled water [22, 23]. The corrosion solution was bubbled using nitrogen gas (N2) for 4 h to

deaerate and kept CO2 passing through for 4 h. The electrochemical experiments were performed with

the CS350 electrochemical measurement system, and a traditional three-electrode cell has been applied

to perform the mentioned electrochemical tests with a temperature of 303 K throughout the

experiment. The reference electrode was a saturated calomel electrode (SCE) and the counter electrode

(CE) was a platinum plate. The specimens of bare P110 steel and G3 alloy-like coating were used as

the working electrode (WE) [22, 23]. The OCP measurements were started after the each sample was

put into the corrosion medium, and the total time was 3600 s. The potentiodynamic polarization of the

sample was swept at a rate of 1 mV/s.

3. RESULTS AND DISCUSSION

3.1 Microstructural characterizations

XRD diffract gram of the obtained coating is suggested in Figure 2, which can help to elucidate

the material transformations that had taken place in the P110 steel surface. Seen from Figure 2, the

diffraction peaks of the coating rather close to the G3 alloy source electrode, it has indicated the

formation of G3 alloy-like coating on P110 steel by DGPSA.

Figure 2. XRD pattern of the G3 alloy, G3 alloy-like coating and P110 steel


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Figure 3 presents the surface morphology (a) and composition (b) of the G3 alloy-like coating.

As exhibited in Figure 3, the G3 alloy-like coating is uniform and continuous. Some protuberances

distribute on the G3 alloy-like coating surface. The protuberances might be resulted from the local

fusion of G3 alloy target which was induced by point discharge [10]. The surface compositions of the

G3 alloy-like coating and G3 alloy source electrode have further confirmed the formation of G3 alloy-like coating by surface EDS scan, as shown in Figure 3(b) and Figure 3(c). As the G3 alloy source

electrode was suspended by thin Mo bar in DGPSA, Mo atoms were bombarded out from the G3 alloy

source electrode and Mo bar which has resulted higher in Mo on the surface G3 alloy-like coating than

that of G3 alloy source electrode.

Figure 3. Surface morphology (a) and composition (b) of G3 alloy-like coating, composition of G3

alloy (c)


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The microstructure of the G3 alloy-like coating on P110 steel was analyzed under an OM on

transverse nital-etched micro-section. A bright, non-etched layer with an estimated thickness of 35 μm

was observed according to the measuring scale, and it was clearly separated from the P110 steel

substrate (Figure 4(a)). GDOES analysis results is shown in Figure 4(b), it is found that the

concentration of Ni and Cr decreased gradually, the composition of Fe increased from the surface toinside [13]. This gradient distributing character of Ni, Cr and Fe elements in the coating has been

found to be helpful to enhance the bonding strength at the interface of the coating and the substrate

[17]. It can be seen in Figure 4(b) that the G3 alloy-like coating reached a thickness of about 35 μm.

Figure 4. Cross-sectional microstructure (a) and composition profile (b) of G3 alloy-like coating

3.2 Wear resistance

According to the measuring points on the surfaces of bare P110 steel and G3 alloy-like coating,

surface hardness column charts were created as shown in Figure 5. The G3 alloy-like coating has

higher hardness value than P110 steel. The higher hardness on the G3 alloy-like coating surface can

also enhance the anti-wear property of P110 steel [24]. Figure 6 illuminates the friction coefficients

of the G3 alloy-like coatings and the P110 steel substrates and against GCr15 and Si 3 N4. Seen from

Figure 6, it is found that the friction coefficients of the P110 steel substrate are lower than those ofthe G3 alloy-like coating. The distinctions can be explained from the following aspects: firstly, the


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ground P110 steel is smooth, and the P110 steel is not as hard as the GCr15 and Si 3 N4 balls, the

friction force between the P110 steel and the counterparts is low; secondly, the protuberances on the

coated surface which have an effect on the surface roughness, increased the friction coefficients;

thirdly, adhesion is prone to occur between a metal-metal friction interface as compared with a

ceramic-metal friction interface, hence the friction coefficients against GCr15 are more fluctuatedthan those of against Si3 N4 [25, 26].

Figure 5. Surface micro hardness values of tested samples

Figure 6. Coefficients of friction of tested samples sliding against GCr15 (a) and Si3 N4 (b)


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Figure 7 compares the differences in mass loss between P110 steel substrates and G3 alloy-like

coatings after dry sliding. It is obviously that the mass losses of the G3 alloy-like coatings (0.02667 mg

and 0.01667 mg) were lower than P110 steel substrates (0.09667 mg and 0.04333 mg). The lower mass

losses of G3 alloy-like coating compared with P110 steel was mainly due to the improvement in

surface hardness degree of the G3 alloy-like coating and the high metallurgical bonding strength [25,26]. Therefore the P110 steel showed higher mass losses than those of the G3 alloy-like coating. It is

allowed to draw a conclusion that the G3 alloy-like coating had significantly improve the wear

resistance of P110 steel.

Figure 7. Mass losses of tested samples sliding against GCr15 and Si3 N4

Figure 8 displays the whole and enlarged SEM images of wear traces for G3 alloy-like coatingand P110 steel after dry sliding against GCr15. EDS analyses for zone 1 and zone 2 in Figure 8(b) are

suggested in Table 2. Zone 1 in grey color reveals high Cr, Ni and Mo content, which means the G3

alloy-like coating was not worn through. Zone 2 in dark color with higher O and Fe contents than zone

1 might have formed in the transfers from GCr15 counterpart. The concentrations of O in zones 1 and

2 as revealed in Table 2 had proved oxidation reactions took place, it was owing to the chemical

reaction of the metal to oxidize. Combining with the mass loss results, the wear mode of G3 alloy-like

coating mainly was the transfer of counterpart to the G3 alloy-like coating associated with oxidation

wear.

Table 2. EDS results of worn G3 alloy-like coating sliding against GCr15

Element (Wt. %) O Cr Fe Ni Cu Mo

Zone-1 14.77 13.65 40.46 18.22 0.06 12.85

Zone -2 37.54 3.45 53.43 3.14 0.01 2.42

As shown in Figure 8(d), the worn P110 steel showed very rough surface, adhesive and

abrasive marks were noticeable. There was high chemical affinity between P110 steel and GCr15 steel,

thus cold welding or adhesion was prone to happen between the friction interface. However, this linkcould be broken by relative sliding of the friction couples [25, 26]. Adhesive wear occurred, which was


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demonstrated by adhesive built-up (zone 2) and detected by EDS in Table 3. The presence of O in zone

1 and zone 2 has revealed the oxidation occurred during dry sliding [25, 26]. The main wear mode of

P110 steel was adhesive wear combined with oxidation wear and abrasive wear.

Table 3. EDS results of worn P110 steel sliding against GCr15

Element (Wt. %) C O Mn Fe

Zone-1 3.37 7.08 1.23 88.32

Zone -2 2.91 37.92 / 59.17

Figure 8. Wear traces of G3 alloy-like coating (a) , (b) and P110 steel (c), (d) sliding against GCr15


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Table 4. EDS results of worn G3 alloy-like coating sliding against Si3 N4

Element (Wt. %) N O Si Cr Fe Ni Cu Mo

Zone-1 0.21 7.18 0.22 20.85 27.85 19.12 0.06 24.51

Zone -2 1.68 40.42 1.08 13.33 16.51 12.96 0.02 13.98

Table 5. EDS results of worn P110 steel sliding against Si3 N4

Element (Wt. %) C N O Si Mn Fe

Zone-1 2.35 0.78 12.62 0.9 1.24 82.12

Zone -2 1.94 1.33 30.77 1.98 / 63.99

Figure 9. Wear traces of G3 alloy-like coating (a), (b) and P110 steel (c), (d) sliding against Si3 N4


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Figure 11. Polarization curves of tested samples

Figure 11 shows the potentiodynamic polarization curves of P110 steel and G3 alloy-like

coating in CO2-saturated simulated oilfield brine. Seen from Figure 11, P110 steel shows no passive

zone, its anodic current increases with increasing polarization. After the polarization test of P110 steel,

the corrosion medium became yellowish green, indicating the severe corrosion of P110 steel [27 – 31].

As shown in Figure 11, it can also be seen that the anodic branch of the polarization curve of G3 alloy-

like coating is characterized by a passive region (from 0 V to 0.79 V) and breakdown potential (small

circle marked). The existence of passive region for the G3 alloy-like coating reveals that the passive

film has naturally formed when it was exposed to the corrosive electrolyte. By using the Tafel

extrapolation method, the values corrosion current density for G3 alloy-like coating and P110 steel are

3.957×10-6 A/cm2 and 2.505×10-5 A/cm2, respectively [27 – 31]. The G3 alloy-like coating significantly

enhanced the corrosion resistance of P110 steel.

4. CONCLUSIONS

In this work, continuous and compact G3 alloy-like coating has been fabricated on P110 steel

by employ of DGPSA. The G3 alloy-like coating exhibited higher surface hardness value and lower

mass losses than those of P110 steel. G3 alloy-like coating showed no obvious friction-reduction

effect, but revealed good wear resistance with the lower mass losses. G3 alloy-like coating held higher

OCP and lower current density as compared with P110 steel; it presented excellent corrosion resistance

in CO2-saturated simulated oilfield brine.

ACKNOWLEDGEMENTS

This work was supported by the Science and Technology Programs for Research and Development of

Shaanxi Province (No. 2013KJXX-08), the National Natural Science Foundation of China (No.

51474154), the China Postdoctoral Science Foundation (No.2012M520604), the Natural Science

Foundation for Young Scientists of Shanxi Province (No.2013021013-2, No. 2014011036-1).

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Fabrication of Wear and Corrosion Resisting G3 Alloy-like P110 (2015)

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